All purpose detergent bar



ALL PURPOSE DETERGENT BAR No Drawing. Application May 12, 1953, Serial No. 354,647

9 Claims. (Cl. 252-161) This invention relates to the production of a detergent bar or cake and more particularly to an all purpose dctergent bar suitable for use in soft water, hard water and sea water.

It is known that either hard water or sea water seriously impairs the efiiciency of soap in regard to detergency and lathering due to the precipitation of the calcium and magnesium salts of soaps. The addition of synthetic detergents to soap to improve performance in hard and sea water is an art that has been practiced for many years but the major objection to such combinations is poor lather. On the other hand, non-soap-containing synthetic detergent bars are not satisfactory due to high cost, hygroscopicity, unsatisfactory solubility characteristics, defatting action on the skin, lack of lubricating effect and slippery feel usually associated with soap, poor working properties in standard soap machinery, brittleness and poor cohesion of the bar itself. A large number of binders and tillers have been used in conjunction with synthetic detergents in an attempt to obtain a detergent bar resembling in activity the usual toilet soap bar when used in soft water. However, although a considerable amount of work has been done to provide an all purpose detergent bar, none has been truly satisfactory. The following may be considered to be the major properties desirable in a good all purpose detergent bar.

1. Good detergency on the human skin, and fabrics and hard surfaces in all kinds of Water including hard, soft, sea, cold and hot.

2. Good soap-like lathering qualities in all types of water, particularly when used on the skin.

3. Mild and non-injurious to the skin.

4. Little or no tendency towards softening, blooming, crystallizing, cracking, drying or decomposing under ordinary use and storage conditions.

5. Pleasing appearance, feel and odor.

6. Ability to be produced in standard soap-mixing equipment.

Attempts to provide an all purpose detergent bar with the aforementioned properties are complicated and rendered difficult by the following facts.

1. Detergents which foam poorly at the lower concentrations commonly used in standard foam tests frequent-1y lather copiously when used at higher concentrations such as is obtained in washing the hands.

2. All ingredients in the bar should have approximately the same rate of solubility or dispersibility in order to prevent pitting, grittiness and the like.

3. The rate of solubility should be approximately the same in cold water as it is in hot water, and should not be unduly high in order to prevent rapid dissolution when left in water.

4. Some detergents leave sticky or other objectionable residues on the skin.

5. Calcium and magnesium salts of fatty acids formed in situ will seriously impair the lather of many sur factants in certain concentration ranges.

6. Many surfactants which have satisfactory detergent nited States Patent and lathering properties when used in soft water, have unsatisfactory properties in hard water and sea Water. This also applies to soap.

7. Many surfactants which have good detergent and foaming properties by themselves are unsatisfactory when mixed with soap and certain other surfactants.

It is an object of this invention to provide an all purpose detergent bar which will possess substantially all of the above mentioned major properties desirable in a good all purpose detergent bar. it is another object of this invention to provide a detergent bar capable of producing a satisfactory lather in hot and cold, soft, hard and sea Water. It is still another object of this invention to provide an all purpose detergent bar which will be non-toxic and non-irritating to the human skin. A still further object of this invention is to provide a detergent bar capable of satisfactory performance in water of any degree of hardness from zero to the hardness of sea Water and at any temperature of from 0 C. to 100 C. for Washing dishware and kitchen utensils and the like, for hand laundering of clothing, for use as a general purpose toilet soap, and for shaving purposes. Still another object of this invention is to provide a detergent bar having the properties of a good grade of soft water toilet soap. Other objects and advantages will appear as the description proceeds.

The above objects are attained by the instant invention which is directed to the production of a detergent bar comprising (A) a synthetic organic anionic detergent selected from the group consisting of the water soluble alkali metal and amine salts of higher aliphatic sulfates and sulfonates containing a hydrocarbon radical with at least 11 carbon atoms in a straight chain, and alkyl aryl sulfates and sulfonates containing at least one alkyl side chain radical of at least 8 carbon atoms, and (B) a waterinsoluble compound selected from the group consisting of higher fatty acids and their polyvalent metal salts. Optionally and preferably the detergent bar may also contain at least one synthetic organic anionic lathering agent selected from the following groups C and D, group C consisting of the water-soluble alkali metal and amine salts of lower alkyl aryl sulfates and sulfonates containing at least one alkyl side chain radical of from 2 to 6 carbon atoms, and group D consisting of similar salts of lower aliphatic sulfates and sulfonates containing an open (straight or branched) chain hydrocarbon radical of from 3 to 9 carbon atoms. More preferably, one lathering agent from each of groups C and D are employed in the detergent bar. The detergent bar may also contain suitable binders, fillers, perfumes, salts, colors, fungicides, germicides, antiseptics and the like.

As the long chain detergents suitable for use as component A in the instant invention, there may be mentioned long chain alkyl aryl sulfonates such as sodium octyl-, nonyl-, dodecyl-, decyland tetradecylbenzene sul fonates, N-long chain acyl N-alkyl taurates such as sodium oleoyl methyl taurate, sodium palmitoyl methyl taurate, sodium lauroyl methyl taurate, and the corresponding acyl ethyl taurates, long chain alkyl oxyethylene sulfates such as sodium or potassium laurylpolyoxyethylene sulfate, sodium lauryl monoxyethylene sulfate, sodium octadecylpolyoxyethylene sulfate, and sodium cetylpolyoxyethylene sulfate, long chain alkyl aryl oxyethylene sulfates such as ammonium, sodium, or potassium nony-, octyland tridecylphenol mono and polyoxyethylene sulfates, long chain alkyl sulfates such as sodium lauryland stearyl sulfates, long chain alkyl isethionates such as sodium oleic isethionate, sodium lauric isethionate, and the like. Mixtures of the above mentioned detergents may also be employed. Component A may be used in quantities varying from about 5 to percent, but preferably from about 5 to 50 percent by weight of the bar.

As the water-insoluble compound for use as component B in the instant invention may be mentioned fatty acids of at least 9 carbon atoms and their calcium, magnesium, zinc and aluminum salts. Representative of the fatty acids which may be employed are myristic, palmitic, stearic, behenic, oleic, lauric, capric, caproic, ricinoleic, linoleic acids and the like and the surface active hydrolysis products of tallow, cocoanut oil, cottonseed oil, soy-bean oil, peanut oil, sesame, linseed oil, olive oil, corn oil, castor oil and the like. All of these compounds are water-insoluble at room temperature. Component B may be used in amounts varying from about 10 to 90 percent, but preferably from about 15 to 65 percent by weight of the bar.

The suitability of the aforementioned water-insoluble compounds for use in providing an all purpose detergent bar with improved properties was indeed surprising since the formation in situ of insoluble salts, mixed salts or complexes of soap and anionic detergents have a well known deleterious effect on lathering. It was even more surprising that when such Water-insoluble compounds were employed in the detergent bar instead of water-soluble soaps, the amount of synthetic detergent could be reduced substantially without any loss in the amount of lather produced.

As the lower alkyl aryl lathering agent suitable for use as component C in the instant invention there may be mentioned sodium diisopropyl naphthalene sulfonate, sodium isopropyl naphthalene sulfonate, sodium diisobutyl naphthalene sulfonate, sodium isobutyl naphthalene sulfonate, sodium isohexylbenzene sulfonate, monobutyl biphenyl sodium monosulfonate, monobutylphenylphenol sodium rnonosulfonate, dibutylphenylphenol sodium disulfonate, and the like. Component C may be used in quantities ranging from about to 75 percent, but more preferably from about to 25 percent by weight of the bar.

As the lower aliphatic lathering agent suitable for use as component D in the instant invention there may be mentioned the lower alkyl sulfates and sulfonates such as the sodium sulfate derivative of 2-ethyl hexanol-l, sodium Z-ethyl-l-hexenyl sulfonate, sodium isooctyl sulfonate and sodium isononyl (also triisopropylene) sulfonate, lower alkyl esters of aliphatic sulfopolycarboxylic acids such as sodium diamyl sulfosuccinate, sodium diisobutyl sulfosuccinate, sodium dihexyl sulfosuccinate, sodium dioctyl sulfosuccin-ate, sodium triamyl sulfotricarballylate, sodium tn'isobutyl sulfotricarballylate, and sodium tri-n-butyl sulfotricarballylate, and the like. Component D may be used in quantities ranging from about 0 to 75 percent but more preferably from about 5 to 25 percent by weight of the bar.

While the water-soluble sodium salts of the aforementioned detergents and lathering agents are generally preferred, other alkali metal and amine salts may be employed, as for example those with potassium, ammonium, lower alkyl amines such as methylamine, ethylamine, propylamine, and isopropyl amine, lower alkylolamines such as mono-, diand triethanoland isopropanolamines, cyclic amines such as cyclohexylamine, morpholine, pyrrolidine and the like.

Suitable additives, e. g. binders, fillers, builders and the like may be added to the detergent bar of the instant invention to provide properties regarded as desirable in any particular instance. These may include polyethylene glycol, starch (substituted, degraded or undegraded), soaps, lignin, alignates, and copolymers of maleic anhydride with styrene and polyvinyl alkyl ethers and the like, in addition to urea, zein, lecithin, lanolin, carboxymethylcellulose, talc, salts such as borax, calcium chloride, magnesium chloride, sodium sulfate, sodium phosphate, tetrasodium pyrophosphate and sodium tripolyphosphate, oxides and hydroxides such as magnesium oxide, sodium hydroxide, potassium hydroxide and titanium hydroxide, dyes, pigments, perfumes and the like.

These supplementary agents may be used to control the rate of solubility of the bar, improve slip and feel, stabilize it against changes in humidity which cause softening or drying out, improve its appearance and odor, serve as builders and the like. Their use however must be carefully regulated to prevent undesirable and disadvantageous properties from resulting. Thus, some inorganic salts are too soluble and are leached out of the bar, making it rough. Others are insoluble or only slightly soluble so that they are left as rough gritty particles on the surface of the bar when the more soluble portions are dissolved out. Many crystallize out on the surface of the bar during storage. Some are too hygroscopic, causing excessive softening of the bar on storage in humid conditions. Most of them make a very hard and dense bar. Those with a negative heat of solution make the bar feel cold on the skin during use. Varying amounts of inorganic salts such as sodium sulfate, sodium chloride, ammonium chloride and the like are present in certain of the surfactants employed in the bar as manufactured, but generally and preferably such amounts total no more than about 25 percent by weight of the bar. Bars containing clay, bentonite or rosin usually have a gritty feel and insufficient slip. Some are very dark in color making a very unattractive bar.

Small amounts of waxes, oils, fats and greases improve milling of the ingredients by plasticizing the mixture. They also serve as lubricants in aiding release of the bar from the dye in the stamping operation. Residues left on the skin after washing act as emollients to overcome the defatting eflect of the detergents. However, they have a serious defoaming effect on the surfactants in the composition particularly when employed in too large an amount. Carboxymethylcellulose may be added to improve whiteness retention for fabric detergency and as a foam stabilizer and skin beneficicnt. Similarly, lanolin when used in emollient amounts to overcome the defatting effect of the detergents, has a detrimental effect on lathering properties.

Starches, gums and dextrines are unsatisfactory in large amounts in that they tend to reduce the slip of the bar and dry out, causing cracking and crumbling of the bar. Those of low solubility are preferred since they reduce the rate of consumption of the bar.

In the preferred embodiment of this invention, the detergent bar contains a mononuclear long chain alkyl aryl sulfonate, more specifically sodium dodecylbenzene sulfonate, as component A, a water insoluble polyvalent metal salt of a higher fatty acid, more specifically calcium stearate, as component B, a lower alkyl naphthalene sulfonate, more specifically sodium diisopropyl naphthalene sulfonate, as component C, and a lower alkyl ester of an alpihatic sulfopolycarboxylic acid, more specifically sodium diamyl sulfosuccinate, as component D, in addition to a gum such as degraded corn starch and a small amount of carboxymethylcellulose. A bar manufactured in accordance with this preferred embodiment has highly satisfactory properties for handwashing, shaving, dishwashing and cotton detergency in soft, hard or sea water, and possesses the property of excellent storage stability.

The bar in accordance with the instant invention may be produced in well known manner by a framing, milling or similar process. In making frame bars, all the ingredients are mixed at elevated temperatures in a crutcher with sufficient water to permit easy stirring. The mass is then poured into wooden frames to cool, solidify and partially dry after which the frame is removed, and the soap block out into pieces and stamped in a soap press. In the milling process all of the materials for making the bar are mixed in an amalgamator, preferably passed through a roller mill for one or more times to assure a thorough mixing while adding suflicient water to provide the proper viscosity, and the milled mass then compressed and extruded from a plodder into long bars which are cut into suitable lengths and stamped into the-desired shape and size.

The examples in the following table, in which parts 2,781,821 5 are by weight, are illustrative of the compositions of .the detergent bars made in accordance with the instant invention. It will be understood that the invention is not limited thereby.

6 While all of the detergent bars described in the table are satisfactory, that of Example 7 containing the preferred components, as described above, possesses superior properties. The bars of Examples 1, 4, 8, 10, 11, 18

Table Detergent Fatty Acid Compound Lathering Agents Additional Components A B O D Ex. Type Parts Type Parts 'lype Parts Type Parts Type Parts 1 Na lauroylmothyl 10 Ca stearate.. 50 Nadiisopropylnaphl Dex.No.162 20 taurate. tbalcne sulfonate. 2 Naotleoylmethyltaw 7 do 50 do .e 10 23 re e. .3 Naoleiclsethionatm. 6 ..do 50 .do r. 10 24 4 NH; nonylphenol 10 do 50 do 10 20 (C2H40)4 sulfate. 5 Na lauroylmethyl do 50 Na diamylsulfo- 5 GumNo.198

taurate. suecinate. H 6 NH; nonylphenol 10 .do 5O do e- 5 do \T ci i 1i N d" 1 h V G N 19s 13 L a o ecy enzene a nsopropy nap um o. 7 snlfonate. 10 50 thalcnesultonnte. 1O "F 5 {CarboseD 2 s "was 10 d0 so .do 10 do s {gg g iq-ji j 9 Na lauroylmethyl 75 ...do 25 taurate. 10 Na dodecylbenzene .do 25 .2 Na diatnyl sultosullonate. I succinate. 11 d 25 do 25 Nadiisopropylnaph- 25 thalene sulfonate.

12 H.410 do r. 25

Na diisopropyl naph- Na diamyl sulfo- 13 10 28 thalene suhonate. 10 succinate. 14 .do 10 do 10 do 5 S'IPP 15 do 10 do 10 Z-ethyl-I-hexanol 13 Gum No. 198.. 17

Na sulfate. 10 do e. 10 ..do 20 d0 10 10 do 10 Na isooctyl sulto- 10 do 10 note. 10 do 10 Nalsononylsullo- 14 note. 10 Mgstearat0 10 Na diamyl sulfosuecinate. 1O Alstearate. 10 Znstoaratd...

10 Castearatcuu 23 Nalaurieisethionate. 45

25 do 4s 26 Na dodecylbenzene 20 Na diisopropylnaphsulfonate. thalene sulfona to.

20 10 20 10 20 10 20 Neotatl-GS... 0 N u 5 10 Casts/amen 5 {sii iaffffiifji i5 15 do 7 Natallowsoapn 26 All of the detergent bars described in the above table have satisfactory handwashing lathering properties in tap water and as good or better lathering properties in sea water with the exception of the bar of Example 12 which contains no lathering agent C or D and is excellent in hard and soft waters but is somewhat inferior in sea water. However it is superior to a similar sodium soap dodecyl benzene sulfonate combination. The parts of sodium dodecylbeuzene sulfonate shown in the table comprise about 85 percent of active ingredient and 15 percent of inert ingredients, such as sodium sulfate. The parts of sodium diisopropyl naphthalene sulfonate shown in the table comprise about percent of active ingredient and 45 percent of inert ingredients such as sodium sulfate. The parts of sodium oleoyl and lauroyl methyl taurates shown in the table comprise about 70 percent of active ingredient and 30 percent of inert ingredients such as sodium chloride. The parts of sodium oleoyl and lauroyl isethionates shown in the table comprise about 85 percent of active ingredient and 15 percent of inert ingredients such as sodium chloride. Dex. No. 162 and Gum No. 198 are degraded corn starches. Carbose D is carboxymethylcellulose. STPP is sodium tripolyphosphate. Alcolec S is lecithin. Neo Fat 1-60 is 75 percent stearic, 22 percent palmitic and 3 percent oleic acids. Neo Fat-L65 is 90 percent stearic, 6 percent palmitic and 4 percent oleic acids.

through 21, and 23 through 27 also have highly satisfactory properties.

It will be understood that the term detergent bar as employed herein and in the appended claims includes any detergent composition in a solid cohesive state in any size or shape; Similarly the recitation of an alkyl or hydrocarbon radical containing a specified number of carbon atoms is to be considered as also including a mixture of radicals of the same type averaging the specified number of carbon atoms. Various modifications and variations of this invention will be obvious to a person skilled in the art, and it is to be understood that such modifications and variations are to be included within the purview of this application and the spirit and scope of the appended claims.

What is claimed is:

1. A detergent bar comprising, by weight, (A) about 5 to 50% of a synthetic organic anionic detergent selected from the group consisting of the water-soluble alkali metal and amine salts of an alkylbenzene sulfonate containing at least one alkyl side chain radical of at least 8 carbon atoms, (B) about 15 to 65% of a water-insoluble salt of a higher fatty acid of at least 9 carbon atoms with a polyvalent metal selected from the group consisting of calcium, magnesium, zinc and aluminum, (C) about 5 to 25% of a synthetic organic anionic lathering agent selected from the group consisting of the water-soluble alkali metal and amine salts of an alkylaryl sulfonate containing at least 1 alkyl side chain radical of from 2 to 6 carbon atoms and devoid of alkyl side chain radicals of more'than 6 carbon atoms, and (D) about to 25% of a synthetic organic anionic lathering agent selected from the group consisting of the water-soluble alkali metal and amine salts of a lower alkyl ester of a lower aliphatic sulfopolycarboxylic acid containing an open chain radical of from 3 to 9 carbon atoms.

2. A detergent bar as defined in claim 1 in which component A is sodium dodecylbenzene sulfonate.

3. A detergent bar as defined in claim 1 in which component B is the calcium salt of a higher fatty acid.

4. 'A detergent bar as defined in claim 1 in which component C is sodium diisopropyl-naphthalene sulfonate.

5. A detergent bar as defined in claim 1 in which component D is sodium diamylsulfosuccinate.

6. A detergent bar comprising, by weight, about 5 to 50% of sodium dodecylbenzene sulfonate, about 15 to 65% of a water-insoluble salt of a higher fatty acid of at least 9 carbon atoms with a polyvalent metal selected from the group consisting of calcium, magnesium, zinc and aluminum, about 5 to 25% of sodium diisopropylnaphthalene sulfonate, and about 5 to 25% of sodium diamylsulfosuccinate.

7. A detergent bar as defined in claim 6 in which said water-insoluble salt is calcium stearate.

8; A detergent bar comprising, by weight, about 10 parts of sodium dodecylbenzene sulfonate, about parts of calcium stearate, about 5 parts of sodium diisopropylnaphthalene sulfonate, and about 5 parts of sodium diamylsulfosuccinatc.

9. A detergent bar comprising, by Weight, about 10 parts of sodium dodecylbenzene sulfonate, about 50 parts of calcium stearate, about 5 parts of sodium diisopropylnaphthalene sulfonate, about 5 parts of sodium diamylsulfosuccinate, about 13 parts of degraded corn starch, and about 2 parts of carboxymethyl cellulose.

' References Cited in the file of this patent UNITED STATES PATENTS 1,906,484 Nuesslein May 2, 1933 2,176,423 Jaeger Oct. 17, 1939 2,438,169 Hoyt Mar. 23, 1948 2,462,758 Malkemus Feb. 22, 1949 2,617,772 Kcnnan Nov. 11, 1952 2,631,980 Lewis Mar. 17, 1953 2,678,921 Turck May 18, 1954 FOREIGN PATENTS 592,206 Great Britain Sept. 10, 1947 896,092 France Feb. 12, 1945 

1. A DETERGENT BAR COMPRISING, BY WEIGHT, (A) ABOUT 5 TO 50% OF A SYNTHETIC ORGANIC ANIONIC DETERGENT SELECTED FROM THE GROUP CONSISTING OF THE WATER-SOLUBLE ALKALI METAL AND AMINE SALTS OF AN ALKYLBENZENE SULFONATE CONTAINING AT LEAST ONE ALKYL SIDE CHAIN RADICAL OF AT LEAST 8 CARBON ATOMS, (B) AOUT 15 TO 65% OF A WATER-INSOLUBLE SALT OF A HIGHER FATTY ACID OF AT LEAST 9 CARBON ATOMS WITH A POLYVALENT METAL SELECTED FROM THE GROUP CONSISTING OF CALCIUM, MAGNESIUM, ZINC AND ALUMINUM, (C) ABOUT 5 TO 25% OF A SYNTHETIC ORGANIC ANIONIC LATHERING AGENT SELECTED FROM THE GROUP CONSISTING OF THE WATER-SOLUBLE ALKALI METAL AND AMINE SALTS OF AN ALKYLARYL SULFONATE CONTAINING AT LEAST 1 ALKYL SIDE CHAIN RADICAL OF FROM 2 TO 6 CARBON ATOMS AND DEVOID OF ALKYL SIDE CHAIN RADICALS OF MORE THAN 6 CARBON ATOMS, AND (D) ABOUT 5 TO 25% OF A SYNTHETIC ORGANIC ANICONIC LATHERING AGENT SELECTED FROM THE GROUP CONSISTING OF THE WATER-SOLUBLE ALKALI METAL AND AMINE SALTS OF A LOWER ALKYL ESTER OF A LOWER ALIPHATIC SULFOPOLYCARBOXYLIC ACID CONTAINING AN OPEN CHAIN RADICAL OF FROM 3 TO 9 CARBON ATOMS. 